EP0703249A1 - Oligomers and polymers of amino-alcenes - Google Patents

Abstract

Oligomers (IA) and polymers (IB) are obtd. from 0.001-100 mole-% amino-alkene(s) of formula (II) and 0-99.999 mole-% alkene(s) (III). In (II): x = 0-25; and R<1>-R<6> = H, 1-10C alkyl, 5-7-membered cycloalkyl, opt. with 1-6C alkyl substits., or 6-15C aryl. When (III) is propene is x does not = 1.

Description

• A) 0,001 bis 100 mol-% mindestens eines Aminoalkens der allgemeinen Formel I
  
  in der

  X

  für ganze Zahlen von 0 bis 25 steht und

  R¹ bis R⁶

  Wasserstoff, C₁- bis C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl, das seinerseits C₁- bis C₆-Alkylgruppen als Substituenten tragen kann oder C₆- bis C₁₅-Aryl bedeuten

  und
• B) 0 bis 99,999 mol-% mindestens eines Alkens,
  wobei für x = 1 in Formel I Propen als Komponente B) ausgenommen ist.

The present invention relates to oligomerizates and polymers, obtainable from

• A) 0.001 to 100 mol% of at least one aminoalkene of the general formula I.
  
  in the

  X

  stands for integers from 0 to 25 and

  R¹ to R⁶

  Hydrogen, C₁- to C₁ Alkyl-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry C₁- to C₆-alkyl groups as substituents or are C₆- to C₁₅-aryl

  and
• B) 0 to 99.999 mol% of at least one alkene,
  where for x = 1 in formula I propene is excluded as component B).

Furthermore, the present invention relates to processes for the preparation of such oligomerizates and polymers and their use for the production of further nitrogen-containing polymers.

In many applications for polyolefins, their low polarity is difficult. This is especially true when good surface adhesion is desired, for example when gluing or painting polyolefin-based workpieces. The poor phase connection in polyolefin blends with polar polymers, for example polyamide, is also critical. In order to overcome these difficulties, polyolefin materials are often modified polar, ie polar groups are introduced by suitable surface treatment (for example by flame treatment) or for example by reactive extrusion (for example grafting with MSA). These polar groups chemically bonded to the polyolefin matrix improve the interaction with polar materials and thus the interfacial adhesion.

The various approaches to producing polar-modified polyolefin materials have in common that an expensive post-processing step is required. In addition, the distribution of the reactive groups in the aftertreated polymer is very inhomogeneous and can only be controlled poorly due to the process.

US Pat. No. 3,476,726 describes a copolymer of a 1-olefin with a dialkyl-ω-alkylene amine which can be prepared using a normal, heterogeneous Ziegler-Natta catalyst. However, the polarity of the introduced amino group is significantly reduced by sterically demanding alkyl substituents. It is not possible to split off these substituents with the formation of primary amino groups.

EP-A 423 438 describes the copolymerization of propene with allylbis (trimethylsilyl) amine or diallyltrimethylsilylamine. This is also carried out with a conventional Ziegler-Natta catalyst. In contrast to the copolymers described in US Pat. No. 3,476,726, the trialkyklsilyl protective groups are easily cleaved off solvolytically, so that polyolefin materials having free, primary amino groups are obtained.

A disadvantage of the process described in EP-A 423 438 is the use of a conventional heterogeneous Ziegler-Natta catalyst, since this only allows limited control of the molecular weight distribution and the comonomer distribution.

The object of the present invention was therefore to provide polymers with functional groups, the functional groups introduced being to be distributed as evenly as possible along the polymer chain. Furthermore, the protected functional groups should allow simple removal of the protective groups and the molecular weight distribution of the polymers should be narrow.

We have found that this object is achieved by the oligomerizates and polymers defined at the outset.

Furthermore, processes for the production of such oligomerizates and polymers and their use for the production of further nitrogen-containing polymers have been found.

To produce the oligomerizates and polymers according to the invention, 0.001 to 100 mol%, preferably 1 to 30 mol%, of an aminoalkene of the general formula I in which x preferably represents integers from 1 to 18, in particular from 2 to 15 and R¹ to R⁶ are preferably linear or branched C₁ to C₁₀ alkyl groups, in particular C₁ to C₆ alkyl groups. Preferred compounds of the general formula I are those in which the two silyl radicals -SiR¹R²R³ and -SiR⁴R⁵R⁶ are the same. It is particularly preferred if the radicals R¹, R² and R³ and R⁴, R⁵ and R⁶ have the same meaning, in particular methyl.

Various aminoalkenes can also be used as component A).

wie im Journal of Chem. Soc. 65 (1943), 1075-1080, beschrieben, die entsprechende Chlor-Verbindung

herstellen und diese wie in der Angewandten Chemie 80 (1968), 986-996 zu

umsetzen.The preparation of the aminoalkenes of the general formula I is known per se. For example, you can start from the commercial connections

as in the Journal of Chem. Soc. 65 (1943), 1075-1080, describes the corresponding chlorine compound

produce and this as in Angewandte Chemie 80 (1968), 986-996

implement.

erhalten, welches dann wie in Tetrahedron Letters No. 11 (1968), 1325-1328, beschrieben, zum gewünschten Aminoalken der allgemeinen Formel I umgesetzt werden kann.From this alkenyl phthalimide can then, as described in Synthesis 1976, 389-391, the alkenylamine

received, which then as in Tetrahedron Letters No. 11 (1968), 1325-1328, can be converted to the desired aminoalkene of the general formula I.

0 to 99.999 mol%, preferably 70 to 99 mol%, of at least one alkene are used as component B). Alk-1-enes, in particular having 2 to 28 carbon atoms, preferably having 2 to 10 carbon atoms, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene and decene are preferred. However, cycloolefins having 4 to 10 carbon atoms can also be used, for example cyclobutene and cyclopentene, and bi- and polycyclic olefins such as norbornenes.

In the preparation of the oligomerizates and polymers according to the invention, it has proven to be preferred if components A) and B) are oligomerized or polymerized in the presence of a metallocene catalyst system.

in der die Substituenten folgende Bedeutung haben:

M

Titan, Zirkonium, Hafnium, Vanadium, Niob oder Tantal,

X

Fluor, Chlor, Brom, Iod, Wasserstoff, C₁- bis C₁₀-Alkyl, C₆- bis C₁₅-Aryl oder -OR¹²,

wobei R¹²

C₁- bis C₁₀-Alkyl, C₆- bis C₁₅-Aryl, Alkylaryl, Arylalkyl, Fluoralkyl oder Fluoraryl mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest bedeutet,

R⁷ bis R¹¹

Wasserstoff, C₁- bis C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl, das seinerseits ein C₁- bis C₆-Alkyl als Substituent tragen kann, C₆- bis C₁₅-Aryl oder Arylalkyl, wobei gegebenenfalls auch zwei benachbarte Reste gemeinsam für 4 bis 15 C-Atome, bevorzugt 8 8bis 15 C-Atome, aufweisende cyclische Gruppen stehen können, oder Si(R¹³)₃ mit

R¹³

C₁- bis C₁₀-Alkyl, C₆- bis C₁₅-Aryl oder C₃- bis C₁₀-Cycloalkyl,

Z

für X oder steht,

wobei die Reste

R¹⁴ bis R¹⁸

Wasserstoff, C₁- bis C₁₀-Alkyl, 5- bis 7-gliedriges Cycloalkyl, das seinerseits ein C₁- bis C₁₀-Alkyl als Substituent tragen kann, C₆- bis C₁₅-Aryl oder Arylalkyl bedeuten und wobei gegebenenfalls auch zwei benachbarte Reste gemeinsam für 4 bis 15 C-Atome, bevorzugt 8 bis 15 C-Atome, aufweisende cyclische Gruppen stehen können, oder Si(R¹⁹)₃ mit

R¹⁹

C₁- bis C₁₀-Alkyl, C₆- bis C₁₅-Aryl oder C₃- bis C₁₀-Cycloalkyl,

oder wobei die Reste

R¹⁰ und Z

gemeinsam eine Gruppierung -[Y(R²⁰)₂]_n-E- bilden, in der

Y

für Silicium, Germanium, Zinn oder Kohlenstoff steht,

R²⁰

für Wasserstoff, C₁- bis C₁₀-Alkyl, C₃- bis C₁₀-Cycloalkyl oder C₆- bis C₁₀-Aryl

n

für die Zahlen 1, 2, 3 oder 4

E

für

oder A steht, wobei A ―O―, ―S―, NR²¹ oder PR²¹ bedeutet,

mit R²¹

C₁- bis C₁₀-Alkyl, C₆- bis C₁₅-Aryl, C₃- bis C₁₀-Cycloalkyl, Alkylaryl oder Si(R²²)₃

mit R²²

C₁- bis C₁₀-Alkyl, C₆- bis C₁₅-Aryl, C₃- bis C₁₀-Cycloalkyl oder Alkylaryl.

Particularly suitable metallocene complexes C) can be characterized by the following general formula II:

in which the substituents have the following meaning:

M

Titanium, zirconium, hafnium, vanadium, niobium or tantalum,

X

Fluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl or -OR¹²,

where R¹²

C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,

R⁷ to R¹¹

Hydrogen, C₁ to C₁₀ alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C₁ to C₆ alkyl as a substituent, C₆ to C₁₅ aryl or arylalkyl, optionally also two adjacent radicals together for 4 to 15 C atoms, preferably 8 8 to 15 C atoms, can have cyclic groups, or Si (R¹³) ₃ with

R¹³

C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl or C₃ to C₁₀ cycloalkyl,

Z.

represents X or

being the leftovers

R¹⁴ to R¹⁸

Hydrogen, C₁- to C₁ Alkyl-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C₁- to C₁₀-alkyl as a substituent, mean C₆- to C₁₅-aryl or arylalkyl, and optionally also two adjacent radicals together for 4 up to 15 carbon atoms, preferably 8 to 15 carbon atoms, can have cyclic groups, or Si (R¹⁹) ₃ with

R¹⁹

C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl or C₃ to C₁₀ cycloalkyl,

or being the leftovers

R¹⁰ and Z

together form a grouping - [Y (R²⁰) ₂] _n -E- in which

Y

represents silicon, germanium, tin or carbon,

R²⁰

for hydrogen, C₁- to C₁₀-alkyl, C₃- to C₁₀-cycloalkyl or C₆- to C₁₀-aryl

n

for the numbers 1, 2, 3 or 4

E

For

or A is where A is ―O―, ―S―, NR²¹ or PR²¹,

with R²¹

C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, C₃ to C₁₀ cycloalkyl, alkylaryl or Si (R²²) ₃

with R²²

C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, C₃ to C₁₀ cycloalkyl or alkylaryl.

bevorzugt.
Unter der Bezeichnung Metallocene werden also nicht nur die Bis(η-cyclopentadienyl)-Metall-Komplexe verstanden.Of the metallocene complexes of the general formula II are

prefers.
The term metallocenes does not only mean the bis (η-cyclopentadienyl) metal complexes.

The radicals X can be the same or different, they are preferably the same.

M

Titan, Zirkonium oder Hafnium,

X

Chlor und

R⁷ bis R¹¹

Wasserstoff oder C₁- bis C₄-Alkyl bedeuten.

Von den Verbindungen der Formel IIb sind als bevorzugt diejenigen zu nennen, bei denen

M

für Titan, Zirkonium oder Hafnium steht,

X

für Chlor, C₁- bis C₄-Alkyl oder Phenyl,

R⁷ bis R¹¹

Wasserstoff, C₁- bis C₄-Alkyl oder Si(R¹³)₃,

R¹⁴ bis R¹⁸

Wasserstoff, C₁- bis C₄-Alkyl oder Si(R²⁰)₃ bedeuten.

Of the compounds of the formula IIa, those are particularly preferred in which

M

Titanium, zirconium or hafnium,

X

Chlorine and

R⁷ to R¹¹

Is hydrogen or C₁ to C₄ alkyl.

Of the compounds of the formula IIb, preference is given to those in which

M

represents titanium, zirconium or hafnium,

X

for chlorine, C₁ to C₄ alkyl or phenyl,

R⁷ to R¹¹

Hydrogen, C₁ to C₄ alkyl or Si (R¹³) ₃,

R¹⁴ to R¹⁸

Is hydrogen, C₁- to C₄-alkyl or Si (R²⁰) ₃.

The compounds of the formula IIb in which the cyclopentadienyl radicals are identical are particularly suitable.

Examples of particularly suitable compounds include:
Bis (cyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) diphenyl zirconium,
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride and
Bis (trimethylsilylcyclopentadienyl) zirconium dichloride as well
the corresponding dimethyl zirconium compounds.

R⁷ und R¹⁴

gleich sind und für Wasserstoff oder C₁- bis C₁₀-Alkylgruppen stehen,

R¹⁴ und R¹⁸

gleich sind und für Wasserstoff, eine Methyl-, Ethyl-, iso-Propyl- oder tert.-Butylgruppe stehen

R⁸, R⁹, R¹⁵ und R¹⁶

die Bedeutung
R⁹ und R¹⁶ C₁- bis C₄-Alkyl
R⁸ und R¹⁵ Wasserstoff
haben oder zwei benachbarte Reste R⁸ und R⁹ sowie R¹⁵ und R¹⁶ gemeinsam für 4 bis 12 C-Atome aufweisende cyclische Gruppen stehen,

R²⁰

für C₁- bis C₈-Alkyl,

M

für Titan, Zirkonium oder Hafnium,

Y

für Silicium, Germanium, Zinn oder Kohlenstoff und

X

für Chlor oder C₁- bis C₄-Alkyl stehen.

Of the compounds of the formula IIc, those in which

R⁷ and R¹⁴

are the same and represent hydrogen or C₁ to C₁₀ alkyl groups,

R¹⁴ and R¹⁸

are the same and represent hydrogen, a methyl, ethyl, iso-propyl or tert-butyl group

R⁸, R⁹, R¹⁵ and R¹⁶

the meaning
R⁹ and R¹⁶ C₁ to C₄ alkyl
R⁸ and R¹⁵ are hydrogen
have or two adjacent radicals R⁸ and R⁹ and R¹⁵ and R¹⁶ together represent cyclic groups containing 4 to 12 carbon atoms,

R²⁰

for C₁ to C₈ alkyl,

M

for titanium, zirconium or hafnium,

Y

for silicon, germanium, tin or carbon and

X

represent chlorine or C₁ to C₄ alkyl.

Examples of particularly suitable complex compounds include
Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (indenyl) zirconium dichloride,
Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride,
Ethylene bis (cyclopentadienyl) zirconium dichloride,
Ethylene bis (indenyl) zirconium dichloride,
Ethylene bis (tetrahydroindenyl) zirconium dichloride,
Tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride,
Dimethylsilanediylbis (-3-tert.butyl-5-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-3-tert.butyl-5-ethylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-3-tert.butyl-5-methylcyclopentadienyl) dimethyl zirconium,
Dimethylsilanediylbis (-2-methylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-isopropylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-tert.butylindenyl) zirconium dichloride,
Diethylsilanediylbis (-2-methylindenyl) zirconium dibromide,
Dimethylsilanediylbis (-3-methyl-5-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-3-ethyl-5-isopropylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-2-methylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-methylbenzindenyl) zirconium dichloride and
Dimethylsilanediylbis (-2-methylindenyl) hafnium dichloride.

M

für Titan oder Zirkonium,

X

für Chlor oder C₁- bis C₁₀-Alkyl stehen,

Y

für Silicium oder Kohlenstoff steht, wenn n = 1 ist oder für Kohlenstoff, wenn n = 2 ist

R²⁰

für C₁- bis C₈-Alkyl, C₅- und C₆-Cycloalkyl oder C₆- bis C₁₀-Aryl,

A

für ―O―, ―S―, NR²¹

und

R⁷ bis R⁹

und R¹¹ für Wasserstoff, C₁- bis C₁₀-Alkyl, C₃- bis C₁₀-Cycloalkyl, C₆- bis C₁₅-Aryl oder Si(R¹³)₃ stehen, oder wobei zwei benachbarte Reste für 4 bis 12 C-Atome aufweisende cyclische Gruppen stehen.

In the case of the compounds of the general formula IId, those in which

M

for titanium or zirconium,

X

represent chlorine or C₁ to C₁₀ alkyl,

Y

represents silicon or carbon if n = 1 or carbon if n = 2

R²⁰

for C₁ to C₈ alkyl, C₅ and C₆ cycloalkyl or C₆ to C₁₀ aryl,

A

for ―O―, ―S―, NR²¹

and

R⁷ to R⁹

and R¹¹ represents hydrogen, C₁- to C₁₀-alkyl, C₃- to C₁₀-cycloalkyl, C₆- to C₁₅-aryl or Si (R¹³) ₃, or where two adjacent radicals represent cyclic groups containing 4 to 12 carbon atoms.

Metallocene complexes of the general formula II in which at least one of the radicals R⁷ to R¹¹ is different from hydrogen are particularly preferred. Compounds of the formula IIc are preferably used, in particular dimethylsilanediylbis (-2-methylindenyl) zirconium dichloride and dimethylsilanediylbisindenylzirconium dichloride.

Such complex compounds can be synthesized by methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred.

Examples of corresponding manufacturing processes include in the Journal of Organometallic Chemistry, 369 (1989), 359-370.

Μ-Oxo-bis (chlorobiscyclopentadienyl) zirconium can also be used as the metallocene complex.

As component D), the catalyst systems can also contain open-chain or cyclic alumoxane compounds.

wobei R²³

eine C₁- bis C₄-Alkylgruppe bedeutet, bevorzugt Methyl- oder Ethylgruppe und m für eine ganze Zahl von 5 bis 30, bevorzugt 10 bis 25 steht.

For example, open-chain or cyclic alumoxane compounds of the general formula III or IV are suitable

where R²³

is a C₁ to C₄ alkyl group, preferably methyl or ethyl group and m is an integer from 5 to 30, preferably 10 to 25.

These oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and include in EP-A 284 708 and US A 4,794,096.

As a rule, the oligomeric alumoxane compounds obtained in this way are present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean. The alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls.

It has proven advantageous to use the metallocene complexes and the oligomeric alumoxane compound in amounts such that the atomic ratio between aluminum from the oligomeric alumoxane compound and the transition metal from the metallocene complexes is in the range from 10: 1 to 10 bis: 1, in particular in the range from 10: 1 to 10⁴: 1.

Aromatic hydrocarbons are usually used as solvents for these catalyst systems, preferably with 6 to 20 carbon atoms, in particular xylenes and toluene and mixtures thereof.

The catalyst complexes can also be used in supported form.

The carrier materials used are preferably finely divided carriers which preferably have a particle diameter in the range from 1 to 300 μm, in particular from 30 to 70 μm. Suitable carrier materials are, for example, silica gels, preferably those of the formula SiO₂ · a Al₂O₃, in which a stands for a number in the range from 0 to 2, preferably 0 to 0.5; So these are aluminosilicates or silicon dioxide. Such products are commercially available, e.g. Silica Gel 332 from Grace. Other carriers include finely divided polyolefins, for example finely divided polypropylene.

The preparation of the oligomerizates and polymers according to the invention can be carried out either batchwise or preferably continuously in the reactors customarily used for the oligomerization or polymerization of alkenes. Suitable reactors include Tube reactors, continuously operated loop reactors or stirred tanks, it being possible, if appropriate, to use a number of several stirred tanks connected in series.

The oligo or polymerization conditions are not critical per se. Pressures from 0.5 to 3000 bar, preferably from 1 to 100 bar, and temperatures from -50 ^o C to +300 ^o C, preferably 0 to 150 ^° C, have proved suitable.

The oligomerizations or polymerizations can be carried out in the gas phase, in a suspension, in liquid monomers and in inert solvents. Suitable suspensions or solvents are hydrocarbons, preferably C₄ to C₁₀ alkanes. Oligomers or polymers with good performance properties are also available in the gas phase, in a suspension and in liquid monomers.

The average molar mass of the oligomers or polymers formed can be controlled using the methods customary in polymerization technology, for example by adding regulators such as hydrogen, or by changing the reaction temperatures. By lowering the reaction temperature, oligomers or polymers with increased average molecular weights can be produced.

When the oligomerizates and polymers are worked up, for example by precipitation in hydrochloric acid methanol, the protective groups are simply split off, so that the products have primary amino groups.

The oligomerizates and polymers according to the invention are particularly suitable for the production of further nitrogen-containing polymers. The area of application is very large, for example polyisocyanates, polyurethanes, polyamides and polyureas can be produced.

The oligomerizates and polymers according to the invention are distinguished by uniform incorporation of the functional groups along the polymer chain; in the protected functional groups, the protective groups are simply split off hydrolytically during the workup and the molecular weight distribution of the oligomerizates and polymers is narrow.

Examples Example 1: Polymer from 1-bis (trimethylsilyl) aminoundec-10-ene and propene

In a steel autoclave, 4.4 ml (≙ 11 mmol ≙ 27.9 mol%) of 1-bis (trimethylsilyl) amino-undec-10-ene in 80 ml of abs. Toluene submitted. After adding 20 ml of 10% by weight toluene methylalumoxane solution (Witco), propene was injected to a total pressure of 0.7 bar (≙ 72.1 mol% propene, solubility of propene at 0.7 bar and 40 ° C: 0.2735 mol / l). The polymerization was started by adding a solution of 2.32 mg (≙ 4 μmol) rac-dimethylsilanediylbis (-2-methylbenzindenyl) zirconium dichloride in 4 ml toluene. The temperature was kept constant at 40 ° C. After 4 hours, the polymerization was terminated by relaxing the autoclave. The product was precipitated in methanol.

The work-up afforded 13 g of copolymer having an average molecular weight M _n (number average) of 8446 g / mol (determined by gel permeation chromatography), M _w: M _n of 2.56 and a melting point of 137.6 ^o C. ¹³C-NMR measurements gave a comonomer content (1-bis (trimethylsilyl) amino-undec-10-ene incorporation) of 2.3 mol%. The NMR measurements no longer showed trialkylsilyl groups. Elemental analysis: found: 83.87 C 14.3 H 0.88 N

Example 2: Polymer from 1-bis (trimethylsilyl) amino-undec-10-ene and oct-1-ene

In a steel autoclave 5 ml (≙ 13 mmol ≙ 26.5 mol%) 1-bis (trimethylsilyl) amino-undec-10-ene in 80 ml abs. Toluene submitted. After 10 ml of 10% by weight toluene methylalumoxane solution (Witco) had been added, 5 ml (≙ 0.036 mol) of oct-1-ene were added (≙ 73.5 mol% of oct-1-ene). The reaction was started by adding a solution of 4.15 mg (≙ 9.2 μmol) of dimethylsilanediylbisindenylzirconium dichloride in 4 ml of toluene. The temperature was kept constant at 40 ^o C. The polymerization was terminated after 4 hours.

The workup gave 1.4 g of copolymer with an average molecular weight M _n (number average) of 1160 g / mol (determined by 1 H-NMR spectroscopy). 1 H-NMR measurements showed a comonomer content (1-bis (trimethylsilyl) amino-undec-10-ene incorporation) of 21 mol%. The NMR measurements no longer showed trialkylsilyl groups. Elemental analysis: found: 78.17 C. 13.25 H 2.37 N

Examples 3 and 4: Production of polyureas

1000 mg (≙ 0.63 mmol amino groups) of the copolymer containing primary amino groups obtained in Example 1 were dissolved in 20 ml toluene and with 62.3 mg (≙ 0.63 mmol) n-butyl isocyanate (Example 3) or with 74 , 8 mg (≙ 0.63 mmol) of phenyl isocyanate (Example 4) at 100 ^o C for 60 minutes. It was precipitated in methanol and dried in vacuo for 60 minutes.

Example 3

Elemental analysis: calc .: 82.50 c 14.0 h 1.66 N found: 82.96 C. 14.1 H 1.59 N

Melting point:

142.5 ^o C

Example 4

Elemental analysis: calc .: 82.94 C. 13.76 H 1.64 N found: 83.63 C 13.74 H 1.56 N

Melting point:

143.9 ^o C

The elementary analyzes show the practical quantitative implementation of the components.

Claims (7)

Oligomerizates and polymers, available from A) 0.001 to 100 mol% of at least one aminoalkene of the general formula I.

in the X stands for integers from 0 to 25 and R¹ to R⁶ are hydrogen, C₁- to C₁₀-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry C₁- to C₆-alkyl groups as substituents or are C₆- to C₁₅-aryl and B) 0 to 99.999 mol% of at least one alkene, where for x = 1 in formula I propene is excluded as component B). Oligomerizates and polymers, obtainable from components A) and B) according to claim 1, characterized in that the oligomerization or polymerization in the presence of a catalyst system acting as active components C) a metallocene complex of the general formula II

in which the substituents have the following meaning: M titanium, zirconium, hafnium, vanadium, niobium or tantalum, X fluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl or -OR¹², where R¹² is C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, R⁷ to R¹¹ are hydrogen, C₁ to C₁₀ alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C₁ to C₁₀ alkyl as a substituent, C₆ to C₁₅ aryl or arylalkyl, optionally also two adjacent radicals together can represent cyclic groups having 4 to 15 carbon atoms, or Si (R¹³) ₃ with R¹³ C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl or C₃ to C₁₀ cycloalkyl, Z stands for X or

being the leftovers R¹⁴ to R¹⁸ are hydrogen, C₁- to C₁₀-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C₁- to C₁₀-alkyl as a substituent, are C₆- to C₁₅-aryl or arylalkyl and optionally also two adjacent radicals together can represent cyclic groups containing 4 to 15 carbon atoms, or Si (R¹⁹) ₃ with R¹⁹ C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl or C₃ to C₁₀ cycloalkyl, or being the leftovers R¹⁰ and Z together form a grouping - [Y (R²⁰) ₂] _n -E- in which Y stands for silicon, germanium, tin or carbon, R²⁰ for hydrogen, C₁ to C₁₀ alkyl, C₃ to C₁₀ cycloalkyl or C₆ to C₁₅ aryl n for the numbers 1, 2, 3 or 4 E for

or A is where A is ―O―, ―S―, NR²¹ or PR²¹, with R²¹ to C₁ C to C₁₀ alkyl, C₆ to C₁₅ aryl, C₃ to C₁₀ cycloalkyl, alkylaryl or Si (R²²) ₃ with R²² C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, C₃ to C₁₀ cycloalkyl or alkylaryl and D) contains a compound forming metallocenium ions,
is carried out. Oligomerizates and polymers according to claims 1 to 2, characterized in that as component D) open-chain or cyclic alumoxane compounds of the general formula III or IV

wherein R²³ represents a C₁ to C₄ alkyl group and m represents an integer from 5 to 30, be used. Oligomerizates and polymers according to claims 1 to 3, characterized in that alk-1-enes are used as component B). Oligomerizates and polymers according to claims 1 to 4, characterized in that they are crystalline. Process for the preparation of oligomerizates and polymers according to claims 1 to 5, characterized in that components A) and B) at pressures from 0.5 to 3000 bar and temperatures from -50 to +300 ^o C in the presence of a catalyst system which contains as active components metallocene complexes of the general formula II and optionally open-chain or cyclic alumoxane compounds of the general formula III or IV, are oligomerized or polymerized. Use of oligomerizates or polymers according to claims 1 to 5 for the production of nitrogen-containing polymers.